Process comprising reaction with elemental phosphorus and reaction product thereof

ABSTRACT

ORGANOPHOSPHORUS COMPOSITONS PRODUCED BY REACTING (A) ELEMENTAL PHOSPHORUS, (B) AN EPOXIDE OR AN EPISULFIDE, AND (C) AN ALCOHOL OR A MERCAPTAN, IN THE PRESENCE OF A CATALYTIC QUANTITY OF A BASE, ARE FURTHER REACTED WITH AN ACTIVATED OLEFIN IN PROPORTIONS, AT A TEMPERATURE, AND FOR A PERIOD OF TIME SUFFICIENT TO ADD SAID ACTIVATED OLEFIN TO SUBSTANTIALLY AL OF THE P-H MOIETIES PRESENT IN SAID ORGANOPHOSPHORUS COMPOSITIONS. THE OLEFIN-MODIFIED COMPOSITIONS CAN BE OXIDIZED TO CONVERT TRIVALENT PHOSPHORUS TO PENTAVALENT PHOSPHORUS. THE COMPOSITIONS HAVE UTILITY AS FLAME-RETARDANT ADDITIVES FOR VARIOUS POLYMERIC SYSTEMS INCLUDING PHENOLIC AND EPOXY RESINS.

United States Patent 3,662,029 PROCESS COMPRISING REACTION WITH ELE-MENTAL PHOSPHORUS AND REACTION PRODUCT THEREOF Chisung Wu, NorthBrunswick, N.J., assignor to Union Carbide Corporation, New York, N.Y.

No Drawing. Original application Feb. 15, 1966, Ser. No. 527,492.Divided and this application May 21, 1969, Ser. No. 826,673

Int. Cl. C07f 9/02, 9/28, 9/40 U.S. Cl. 260920 6 Claims ABSTRACT OF THEDISCLOSURE This application is a division of application Ser. No.527,492, filed Feb. 15, 1966 now abandoned.

ORGANOPHOSPHORUS COMPOSITIONS The invention relates to a process forproducing organo phosphorus compositions, to the compositions producedby said process, and to various derivatives thereof. In one aspect, theinvention relates to a process which comprises reacting elementalphosphorus, an alcohol or mercaptan, and an epoxide or episulfide, inthe presence of a basic catalyst. In another aspect, the inventionrelates to the organophosphorus compositions that are produced by theprocess of the invention, and to various derivatives thereof.

The process of the invention comprises reacting elemental phosphorusWith an alcohol or mercaptan and an epoxide or episulfide in thepresence of a basic catalyst to produce thereby an organophosphoruscomposition.

Elemental phosphorus is employed in the invention. White or yellowphosphorus is preferred, although the less reactive red or blackphosphorus can be used if desired.

The second reactant that is employed is an alcohol or a mercaptan. Anyalcohol or mercaptan that is free of sub stituents that can destroy ordeactivate the base catalyst under the reaction conditions employed canbe used in the invention. Thus, the following classes of alcohols andmercaptans can be employed in the invention:

Hydroxyland mercapto-substituted alkanes and cycloalkanes such asmethanol, ethanol, isopropyl alcohol, nbutanol, pentanol, hexanol,cyclopentanol, cyclohexanol, 2-ethylhexanol, isodecanol, lauryl alcohol,stearyl alcohol, ethylene glycol, propylene glycol, butylene glycol,gycerol, 1,2,6-hexanetriol, pentaerylhritol, xylitol, sorbitol, 1,1,1-trimethylolethane, 1,1,l-trimethylolpropane, methyl mercaptan, butylmercaptan, 1,Z-dithiol-3-hydroxypropane, and the like.

A second desirable class of alcohols are the hydroxyethers includingalkylene oxide adducts of active hydrogen-containing compounds.Illustrative of such alkylene oxide adducts are diethylene glycol,triethylene glycol, dipropylene glycol, dibutylene glycol,polyoxypropylene glycols, polyoxyethylene glycols, mixedpolyoxyethylenepolyoxypropylene glycols, polyoxybutylene glycols in-3,662,029 Ice Patented May 9, 1972 eluding polytetramethyleneoxyglycols, propylene oxide adducts of glycerol, and other ethylene oxide,propylene oxide, or butylene oxide adducts of water, methanol, ethanol,isopropyl alcohol, n-butanol, phenol and alkylphenols, ethylene glycol,propylene glycol, butylene glycol, hydroquinone, glycerol,pentaerythritol, ammonia, alkanolamines, alkylamines, aniline, adipicacid, phthalic acid, and the like. The hydroxyethers are organiccompounds having at least one alcoholic hydroxyl group and at least oneether group, and which preferably contain no non-hydrocarbonsubstituents other than ether oxygen, hydroxyl groups, amino groups(usually tertiary amino groups), carbonyl groups, and carbonyloxygroups. The hydroxyether can be a composition having a very highmolecular weight, for instance, up to about 10,000 or more, althoughpreferably the molecular weight Will be below about 5000 and morepreefrably below about 3500.

A third desirable class of alcohols are aminoalcohols. Illustrative ofsuch alcohols are triethanolamine, triisopropanolamine, tributanolamine,N-methyldiethanolamine, N,N-dimethylethanolamine,N-methyldiisopropanolamine, N,N-dimethylisopropanolamine, Nethyldiethanolamine, N-phenyldiethanolamine, and the like. The preferredaminoalcohols are the N-methyldialkanolamines and theN,N-dimethylalkanolamines.

In addition, many other alcohols can be employed including alcohols thatcontain olefinic unsaturation such as ailyl alcohol, oleyl alcohol,linoleyl alcohol, linolenyl alcohol, and the like. The alcohol that isemployed can thus be selected from many classes of compounds providedthat the alcohol is substantially free of groups that would interferewith the reaction. Such groups to be avoided include carboxylic acidgroups, phenolic hydroxyl, halo, and others that would neutralize orsubstantially weaken the basic catalyst.

The third reactant that is employed in the process of the invention isan epoxide or an episul-fide. Epoxyalkanes are particularly useful,illustrative examples of which include ethylene oxide, propylene oxide,butylene oxide, epoxyhexane, epoxycyclohexane, epoxydecane, and thelike. Also, epithioalkanes are useful, for example, ethylene sulfide,propylene sulfide, and the like, can be employed.

Epoxyalcohols can be employed in the process of the invention as thesole reactant with the elemental phosphorus, thereby supplying the epoxyand the alcohol function in a single compound. Among the usefulepoxyalcohols that can be employed are 4-oxatetracyclo [621.0 .01undecan-9( 10)-ol, glycidol, and the like.

Other types of epoxides can be employed in the invention, includingpolyepoxides, aminoepoxides, epoxides containing olefinic unsaturation,ester groups, ether groups, and the like. Specific illustrative examplesinclude vinylcyclohexene dioxide, vinylcyclohexene monoxide, N-glycidyldiethylamine, epoxidized soybean oil and other such oils, the diglycidyldiether of 2,2-bis (para-hydroxyphenyl) propane,3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexarliecarboxylate,bis(2,3-epoxycyclopentyl) ether, and the The alkylene oxides (i.e.,epoxyalkanes) are the preferred epoxides, although for certain specialtyapplications other epoxides are highly useful.

The proportion of the reactants can vary widely. For example, theproportion of epoxide plus alcohol to phosphorus can vary from about 0.1to about 10, and preferably from about 0.3 to about 3, gram-equivalentsof peoxide plus alcohol per gram-atom of phosphorus. The ratio ofalcohol to epoxide can vary widely, for example, from about 0.1 to about10, and preferably from about 0.3 to about 3, equivalents of alcohol perequivalent of epoxide.

A base catalyst is employed in the invention. Alkali metal and alkalineearth metal bases are useful. Examples include sodium hydroxide,potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesiumhydroxide, barium hydroxide, sodium metal, potassium metal (the alkalimetals will form alkali metal alcoholates in situ), potassium carbonate,sodium ethoxide, magnesium methoxide, and the like. Of the alkali andalkaline earth metal base catalysts, the preferred are the alkali metalalcohol ates formed in situ by reaction of alkali metal with the alcoholreactant. Quaternary ammonium bases are highly desirable catalysts foruse in the invention. Quaternary bases can be generated in situ by theinteraction of an N ,N- dimethylamine and an epoxide, as is illustratedby the quaternary ammonium compound formed by the reaction ofN,N-dimethylamine or N,N-dimethylethanolamine with ethylene oxide orpropylene oxide. Other useful quaternary ammonium bases includetrimethyl-Z-hydroxyethyl ammonium hydroxide or alkoxides (which areformed by reaction of aqueous or alcoholic trimethylamine with ethyleneoxide), trimethylbenzyl ammonium hydroxide or alkoxide, and the like.

The base catalyst is employed in catalytically significant quantities.The actual amount can vary widely since the catalyst can be employed invery small amounts or the catalyst can actually be one of the reactants.Thus, the catalyst can be employed in amounts of from about 0.01 molepercent to about 10 mole percent, and more preferably from about 0.1 to6 mole percent, based on gramatoms of phosphorus present in the reactionmixture.

The process of the invention is carried out by contacting the reactantsin a suitable reaction vessel. The order of addition is not critical.The reaction temperature can vary widely, for instance, elevatedtemperatures of from about 25 C. to about 200 C. are suitable, andtemperatures of from about 44 C. (the melting point of White phosphorus)to about 150 C. are preferred. The reaction is carried out for a periodof time suflicient to produce an organophosphorus composition. Forinstance, reaction times of from about 10 minutes to about 10 hours aresuitable, depending upon temperature, nature of the re actants, and thelike. If desired, an inert organic diluent can be employed for thereaction. Suitable diluents include toluene, methyl isobutyl ketone,dioxane, dimethyl sulfoxide, N,N-dimethylformamide, and the like. -It isusually desirable to blanket the reaction mixture with an inertatmosphere such as nitrogen.

Standard procedures can be employed to recover the product. Forinstance, a convenient method is to first neutralize the catalyst, thenfilter and evaporate the product under vacuum to remove unreactedstarting material, solvents, and the like.

The invention also provides novel organophosphorus compositions that areproduced by the process of the invetnion. The novel compositions areusually mixtures of compounds that can be represented by Formula I:

wherein n is a number having a value of from 1 to 2, wherein X is oxy orthio, wherein R represents the residue after removal of the hydroxylgroup of an alcohol or the sulfhydryl group of a mercaptan, and whereinR represents hydrogen, R XH or R XP(R (XR) wherein m represents a numberhaving a value of from to 2, wherein R represents the residue afterremoval of the epoxy group of an epoxide, and wherein X, R, and R are asdefined above. The compounds represented by Formula I can be relativelysimple compounds having only one or two phosphorus atoms, or they can berelatively high molecular weight materials having up to ten or morephosphorus atoms.

Representative examples of organophosphorus compositions that are withinthe scope of Formula I are the following:

( 01-130 1"-CH2CHOH Formula I includes the organophosphorus compositionsformed by reacting elemental phosphorus with a monohydric alcohol and amonoepoxide. More complex compositions can be formed when polyhydricalcohols and/ or polyepoxides are employed. For example, among thecompounds that can be formed by reacting an alkylene or polyalkyleneglycol, phosphorus, and an alkylene oxide are the following:

(f) HO CH CH OIIPCH CHOH (this compound is within the scope of FormulaI) (g) HOCHCH PO(CH CH O),IICH OHOH CH H H H;

wherein x is 1 or more.

The complex nature of the organophosphorus compositions of the inventionis apparent from the foregoing discussion. Said compositions containP-H, P-C, and P-X C groupings in varying proportions that depend to alimited extent, on the proportion of the reactants. For instance, agreater proportion of epoxide or episulfide compared with alcohol ormercaptan will generally increase the proportion of PC groups over P-X-Cgroups. A relatively large proportion of alcohol or mercaptan in thereaction mixture will result in an increase in P-H groups.

The organophosphorus compositions of the invention are useful materials,particularly as reaction intermediates. For example, the compositionscan be oxidized under mild conditions to convert the P=H groups toP('O)OH groups which can be neutralized with alkylene oxide to form auseful polyol. Such polyols can be employed as epoxy resin hardeners, ascoating intermediates after esterifica tion with drying oil acids, andthe like.

In one desirable embodiment of the invention, the organophosphoruscompositions described above are reacted with an aldehyde in order toconvert substantially all of the phosphinous hydrogen (i.e., hydrogenbonded directly to phosphorus) to hydroxymethyl (including substitutedhydroxymethyl) groups. Many aliphatic and aromatic aldehydes can beemployed for this purpose including formaldehyde, acetaldehyde,propionaldehyde, isobutyraldehyde, benzaldehyde, and the like.Formaldehyde is highly preferred. The aldehyde addition reaction iscarried out simply by adding the aldehyde to the organophosphoruscompositions and contacting until substantially all of the phosphinoushydrogen has been converted to hydroxymethyl groups in accordance withthe reaction:

wherein R represents hydrogen or an aliphatic or aromatic group. Thisreaction, which is usually exothermic, will take place at roomtemperature, although higher or lower temperatures (for example, from 20C. to the boiling point of the aldehyde) can be employed if desired. Atroom temperature, the aldehyde addition reaction Usually takes fromabout 0.1 to about 6 hours, after which the product can be recovered byvacuum evaporation of excess aldehyde. The aldehyde is preferablyemployed in proportions slightly in excess of the amount needed to reactwith all of the phosphinous hydrogen. The aldehyde-modified compositioncan subsequently be oxidized (under mild conditions such as by warmingin air) to convert the organophosphorus groupsto organophosphorus oxidegroups, e.g., in accordance with the reactlon:

wherein the variables are as identified above with respect to Formula I(modified to the extent that phosphinous hydrogen is replaced withhydroxymethyl). Such oxidation has the effect of converting trivalentphosphorus to pentavalent phosphorus.

The reaction of aldehyde with phosphinous hydrogen to form hydroxymethylgroups and the oxidation reaction discussed above are both well knowntypes of reactions.

The aldehyde-modified compositions per se and their oxidized derivativesare polyols having wide utility. For instance, these polyols can bemodified by adding ethyleue oxide to form useful surfactants, they canbe employed as epoxy resin hardeners, they can be esterified with dryingoil acids to form surface coating compositions, and the like.

Another desirable embodiment of the invention resides in the reaction ofthe organophosphorus compositions of the invention with an activatedolefin. An activated olefin will add to the P--H group, as illustratedby the reaction:

wherein R represents a strongly electronegative group. Examples ofactivated olefins include acrylonitrile, acrylamide, methyl acrylate,t-butyl methacrylate, vinyl methyl ketone, vinyl methyl sulfone, and thelike. The reaction conditions employed for the addition of activatedolefin are essentially the same as those used for the aldehyde addition.The reaction is usually exothermic and requires no catalysts.

The compositions to which an activated olefin have been added can beoxidized under essentially the same conditions indicated above withrespect to the aldehydemodified materials.

The activated olefin-modified compositions (both per se and the oxidizedderivatives thereof) are widely useful materials. They can be employedas flame-retardant additives (for various polymeric systems includingphenolic and epoxy resins. They are useful as anti-static agents forthermoplastic polymers, as oil additives, as sequestrants. and the like.

A further desirable embodiment of the invention resides in urethanepolymers produced by reacting an organic polyisocyanate with a polyolcomprising the organophosphorus compositions of the invention and/or thevarious derivatives thereof, in particular, the aldehydemodifiedcompositions.

The organic polyisocyanates which can be employed to produce theurethane polymers include tolylene diisocyanate,bis(4-isocyanatophenyDmethane, the polyisocyanates formed byphosgenation of aniline/ formaldehyde condensation products,bis(Z-isocyanatoethyl)furnarate, xylylene diisocyanate, and many otherorganic polyisocyanates that are well known in the art.

It may be desired to employ one or more additional polyols along withthe phosphorus-containing polyols of the invention. Such additionalpolyols include polyesters, polyethers, polylactones and the like.Specific illustrative examples include polyethers comprising alkyleneoxide (especially ethylene oxide, propylene oxide, or butylene oxide)adducts of glycerol, water, dipropylene glycol, ammonia, 1,2,6hexanetriol, 1,1,1 trimethylolpropane, sorbitol, alpha-methyl glucoside,sucrose, aniline-formaldehyde condensation products,phenol-anilineeformaldehyde condensation products, and the like. Usefulpolyesters include reaction products of ethylene glycol, propyleneglycol, glycerol, 1,1,1-trimethylolpropane, or the like with adipicacid, phthalic acid, or the like. Lact'one polymers include homopolymersof epsilon-caprolactone and copolymers of alkylene oxides andepsilon-caprolactone, and the like.

The polyol or polyol mixture employed will be selected according to theend product desired. For example, for flexible foams, a polyol having anaverage hydroxyl number of from about 40 to 70 is desired, forsemi-flexible foams or for rigid foams, polyols having average hydroxylnumbers of from about 70 to 150 or from about 125 to 7000, respectively,are useful.

The hydroxyl number is defined as the number. of milligrams of potassiumhydroxide required for the complete neutralization of the hydrolysisproduct of the fully acetylated derivative prepared from 1 gram ofpolyol. The hydroxyl number can also be defined by the equation:

where OH=hydroxyl number of the polyol f=average functionality, that isaverage number of hydroxyl groups per molecule of polyol M.W.=averagemolecular weight of the polyol The urethane polymers of the inventioncan take the form of foamed products, elastomers, surface coatings,castings and the like. The foamed products can be produced by theone-shot technique wherein all of the reactants are reactedsimultaneously with the foaming operation, by the prepolymer technique,or by the quasiprepolymer technique, all of which are well known in theart. In producing elastomers and castings, the prepolymer technique isuseful. In the prepolymer technique, the isocyanate is reacted with aslightly less than stoichiometric quantity of polyol to produce aprepolymer having a low percentage (e.g., from 4 to 10 percent) of freeNCO groups. The prepolymer is subsequently converted into an elastomerby reacting with a cross-linking agent having reactive hydrogen atomssuch as a diamine, for instance, a bis(aminochlorophenyl)methane. Inproducing surface coatings, there are several types of known reactiontechniques which can be employed.

The amount of polyisocyanate employed will vary slightly depending uponthe nature of the polyurethane being prepared. In general the total--NCO equivalent to :total active hydrogen equivalent (i.e., hydroxylplus water, if water is present) should be such as to provide a ratio ofabout 1.0 to 1.2 equivalents of --NCO per equivalent of active hydrogen,and preferably a ratio of about 1.05 to 1.1 equivalents of NCO perreactive hydrogen.

When foams are being produced, foaming can be accomplished by employinga small amount of water in the reaction mixture (for example, from about0.5 to 5 weight percent of water, based on total weight of the reactionmixture), or through the use of blowing agents which are vaporized bythe exotherm of the isocyanate-reactive hydrogen reaction, or by acombination of the two methods. All of these methods are known in theart. The preferred blowing agents are water and certainhalogen-substituted aliphatic hydrocarbon which have boiling pointsbetween about 40 C. and 70 C., and which vaporize at or below thetemperature of the foaming mass. Illustrative are, for example,trichloromonofluoromethane, dichlorodifluoromethane,dichloromonofluoromethane, dichloromethane, trichloromethane, and thelike.

The amount of blowing agent used will vary with the density desired inthe foamed product. In general it may be stated that for grams ofreaction mixture containing an average isocyanate/reactive hydrogenratio of about 1:1, about 0.005 to 0.3 mole of gas are used to providedensities ranging from 30 to 1 pounds per cubic foot respectively.

Catalysts can be employed in the reaction mixture for accelerating theisocyanate-reactive hydrogen reaction. Such catalysts include a widevariety of compounds. Among the most useful catalysts are the tertiaryamines and the organic tin compounds. Specific illustrative tertiaryamines include N-methylmorpholine, N,N,N,N-

tetramethyl-l,3-butanediamine, 1,4-diazabicyclo[2.2.2]octane, bis [2-(N,N-dimethylamino ethyl] ether, and the like.

Usef ul organic tin compounds include stannous octoate, stannousacetate, stannous oleate, dibutyltin diacetate, di-

8 marized in Table I. A catalytic amount of potassium metal was added atroom temperature to the alcohol or to the reaction mixture, and then thereaction mixture was heated to reflux while vigorously stirred undernitrobutyltin dilaurate, and the like. Many combinations of gen. Whenphosphorus was completely consumed, the recatalysts can be employed, forinstance, it is useful to action mixture was evaporated under vacuum(0.5 mm. employ one or two tertiary amines in combination with Hg) at40-50 C. to constant weight.

TABLE I Reaction K, per- Temp., Time, Example No. Alcohol M01 5 EpoxideM01 3 cent 0. hr.

2 n-Propanol 1.0 Propylene oxide..- 1.7 2.5 42-46 1 3... Propyleneglycol 1.5 1,2-butylene oxide.-- 1.6 5 56112 2 4.-.. Butanol 1.5Propylene oxide 2 5 42-53 1 5.. sec-Butanol 1. .do 2 5 47-55 1 6..n-Dodecanol 1. do 2 5 47-61 2.5 7 n-Propanol. Epoxide A 1. 2. 5 150-1250.2 8.- Epoxide B 2 2. 5 80440 1 9.- n Propanol- 2 Aminoepoxide 2 2. 554-75 1. 2 10 o 2 EpoxideC' 2 5 53-57 1 11 minoalcohol 2 Propyleneoxide.. 2 5 45-61 0.6 12 Ethanol 5 d0 2.5 h 10 46-66 2. 5

Based on one g. atom of P. b G. atom percent of P. 0 Vinylcyclohexenedioxide. d 4oxatetracyelo[6.2.1.0 ,0 ]undecan-9(10)-ol. 6 N-glyeidyldiethylamine. 1 Vinylcyclohexene monoxide. s N,N-dimethy1 ethanolamine.b Sodium metal.

stannous octoate (in making flexible foams) or dibutyltin EXAMPLE l3dilaurate (in making rigid foams). The catalyst is employed in catalyticamounts such as from about 0.05 weight percent to about 6 weightpercent, based on weight of polyol.

When producing urethane foams, it is useful in most cases to employ asurfactant which serves as a stabilizer in making flexible foams and asa cell size regulator in making rigid foams.Polysiloxane-polyoxyalkylene block copolymers are useful surfactants forthis purpose. Among the polysiloxane polyoxyalkylene block copolymersthat are useful are those that are disclosed in US. Pats. 2,834,- 748and 2,917,480 (Bailey et al.) and 2,846,458 (Haluska). The surfactant isnormally employed in amounts of from about 0.01 to about 2 weightpercent, based on weight of polyol.

An excellent summary of urethane polymer chemistry and technology isfound in the text by Saunder and Frisch, PolyurethaneszChemistry andTechnology, Interscience Publishers, New York, Part I, Chemistry, waspublished in 1963 and Part II, Technology, in 1964.

The urethane polymers of the invention have wide utility. For instance,they can be employed as elastomers, rigid and flexible foams, coatings,and the like. The wide utility as gaskets, sealers, in insulation,cushions and padding, in paints, and the like, of such urethane polymersis well known.

The examples which follow illustrate the invention.

EXAMPLE 1 Potassium alkoxide catalyzed reaction of phosphorus withpropylene oxide and propylene glycol To a 500-ml. four-necked flaskequipped with a stirrer, thermometer, Dry Ice-acetone condenser, and adropping funnel were charged 6.2 gm. of yellow phosphorus and 70 gm. ofpropylene glycol. The mixture was heated to 50 C. under a nitrogenatmosphere, and then cooled gradually with vigorous agitation to preparephosphorus sand. To the mixture was added 35 gm. of propylene oxide, and0.24 gm. of potassium dissolved in 12 gm. of propylene glycol. Afterheating for 5 hours at 35-50 (3., the phosphorus was consumedcompletely, leaving a viscous, colorless liquid having a phosphine odor.

EXAMPLES 212 Potassium alkoxide catalyzed reaction of phosphorus withalcohol-epoxide mixtures Various combinations of alcohols and epoxideswere reacted with white phosphorus under the conditions sum- Potassiummercaptide catalyzed reaction of phosphorus with n-butyl mercaptan andpropylene oxide About 0.5 gm. of yellow phosphorus and 5 ml. ofpropylene oxide were added to a test tube containing about 5 ml. ofn-butyl mercaptan in which 0.05 gm. of potassium metal had beendissolved. Upon warming, the reaction mixture turned deep red. The colorfaded when the phosphorus was consumed. The colorless solution was addedto another test tube containing same reactants ex cept potassium. Again,the red color formation Was observed at room temperature, and uponwarming phosphorus was consumed.

EXAMPLE 14 Reaction of phosphorus with N,N-dimethylethanolamine (DMEA)and propylene oxide or ethylene oxide EXAMPLE 15 DMEA-catalyzed reactionof phosphorus with methanol and propylene oxide A mixture of 6.2 gm. ofyellow phosphorus, 2 m1. of propylene oxide, and 0.9 gm. ofN,N-dimethylethanolamine was heated to 45 C. To the resulting red moltenmixture was added dropwise a mixture of 11.6 gm. of propylene oxide and12.8 gm. of methanol. Phosphorus was completely consumed after 0.5 hourat 4575 C. Evaporation of the reaction mixture gave 18 gm. of a lightyellow, water-insoluble, viscous liquid containing 27% P.

EXAMPLE 16 Formaldehyde derivative of the product from Example 15 Theproduct from Example 15 was treated with 16 ml. of 37% aqueousformaldehyde and then with 6 ml. of 30% hydrogen peroxide. Afterevaporation of the reaction mixture, there was obtained a colorlessviscous liquid having 18.76% P.

In another experiment, the formaldehyde-modified product was oxidized byair until the silver nitrate test for the PH bond was negative. Afterevaporation to constant weight, the product was further treated withpropylene oxide until the acid number was about 3. The final prodnot hada phosphorus content of 17%, corresponding to an overall yield of 95%based on phosphorus.

EXAMPLE 17 Acrylonitrile derivative of the product of Example Theproduct from an experiment similar in all significant respects toExample 15 was reacted exothermically with acrylonitrile. Thecharacteristic infrared absorption band of the P-H group at 3.33 1.disappeared and that of the CN group appeared at 4.45 indicating theconversion of the P-H group to the PCH CH CN group.

EXAMPLE 18 DMEA-catalyzed reaction of phosphorus with methanol and1,2-epoxytetradecane A mixture of 6.2 gm. of yellow phosphorus, 3 ml. of1,2-epoxytetradecane and 0.9 gm. of N,N-dimethyl ethanolamine was heatedto 60 C. Then a mixture of 6.4 gm. of methanol and 42.4 gm. of1,2-epoxytetradecane was added dropwise over a 20 minute period at 50-70C. During the following 20 minutes, an exothermic reaction took placewith a deep red color formation. When the color faded, all phosphoruswas consumed. The reaction mixture was oxidized with an excess of 30%hydrogen peroxide and then evaporated. There was obtained 50 gm. of awhite semisolid which showed surface activity when 10 Rigid urethanefoams were prepared by the one-shot technique using the followingrecipe:

Phr. Phosphorus compound 20 Polyol A 1 80 Surfactant 2 1.5 Dibutyltindilaurate 1.5 Isocyanate (about 5% excess) 95.7 Trichlorofluoromethane34 An 80/20 propylene oxide/ethylene oxide adduct of a 1:1:1 phenol:anilinezformaldehyde condensation product; hydroxyl number was 320.

2 A polysiloxane-polyoxyalkylene block copolymcr.

3 An organic polyisocyanate prepared by phosgenation of an aniline]formaldehyde condensation product having an average of about 2.5aromatic nuclei per molecule.

The rigid foam systems were rated nonburning as shown in Table II.

TEST IL-FLAMMABILITY TEST (AS'IM D1692) Foam containing P-Gompound I IIIII EXAMPLE 20 Preparation of flame retardant cotton fabrics TABLE IIIVertical Wt. Cured, Fabric Add-on, Stiflness Break, Ellipse, bFormulation percent F./min. state a percent warp lbs. m.m. Char, m.A.F., sec.

W 6.1 162 BEL BEL 28 fig "{B 5.3 166 BEL P o 7.7 300/8 g "g f 0grgthanolaranlne 152(5) r ompoun 1 Aerotex Resin MW 10.0 300/8 {g 0Aerotex Accellerator #I5. 3. 38

W= Rinsed with tap water, washed (0.01% Amber Flakes) in a home laundrymachine, and tumole dried; B=Boiled 3 hrs. in

0.5% Amber Flakes and 0.2% sodium carbonate.

b Ellipse flame test; BEL=Burned entire length. 0 Vertical flame test;A.F.=After flaming. d Tetrakis (hydroxymethyl)phosphonium chlorid eTris-l-aziridinylphosphine oxide.

' Modified melamine-formaldehyde condensate sold by American CyanamidCompany.

dissolved in water. The sodium salt of the semisolid was also surfaceactive.

EXAMPLE 19 Preparation of flame retardant rigid foams Threeorganophosphorus products were prepared by potassium alkoxide catalysisas previously described.

Compound I: The reaction product of phosphorus, propylene glycol andpropylene oxide; 13.1% P.

Compound II: Compound I treated with formaldehyde;

Compound III: The reaction product of phosphorus, 1.2-

butylene oxide and propylene glycol was air oxidized EXAMPLE 21Oxidation and esterification of the product from Example 15 and furthertreated with 1,2-butylene oxide; 11.6% P. of based on phosphorus.

What is claimed is:

1. Process which comprises the steps of 1) reacting (a) elementalphosphorus, (b) an epoxide or an epithioalkane, and '(c) an alcohol oran alkanethiol, in the presence of a catalytic quantity of a base, at atemperature within the range of from about 25 C. to about 200 C., toproduce an organophosphorus composition, and (2) reacting the product ofstep 1) with an olefin in proportions, at a temperature and for a periodof time suflicient to add said olefin to substantially all of the P-Hmoieties present in said organophosphorus composition.

2. Process of claim 1 wherein said olefin is acrylonitrile, acrylamide,methyl acrylate, t-butyl methacrylate, vinyl methyl ketone, or vinylmethyl sulfone.

3. Process of claim 1 wherein said olefin is acrylonitrile.

4. Process of claim 1 wherein reactant (b) is an epoxyalkane, whereinreactant (c) is selected from the group consisting ofhydroxyl-substituted alkanes, alkanolamines and hydroxyethers, andwherein the base is selected from the group consisting of alkali metalalkoxides, alkali metal hydroxides, alkaline earth metal hydroxides,alkaline earth metal alkoxides, and quaternary ammonium compounds.

5. Process of claim 1 wherein reactant (b) is ethylene oxide, propyleneoxide, 1,2-butylene oxide, or 1,2-epoxytetradecane, and wherein reactant(c) is propylene glycol, methanol, ethanol, propanol, buranol,dodecanol, or N,N- dimethylethanolamine.

6. The product produced by the process of claim 1.

References Cited Grayson et a1.: Topics in Phosphorus Chemistry, vol. I,J. Wiley and Sons, Inc., New York (1964), pp. 2 and 4.

JOSEPH REBOLD, Primary Examiner R. L. RAYMOND, Assistant Examiner US.Cl. X.R. 260968

